1. Field of the Invention
This invention relates generally to a method for reducing the frequency of air/hydrogen fronts in a fuel cell stack and, more particularly, to a method for periodically injecting hydrogen into a fuel cell stack after system shutdown to consume low levels of oxygen as it diffuses back into the stack, increasing the length of time before the stack contents switch from a hydrogen/nitrogen mixture to an oxygen/nitrogen mixture.
2. Discussion of the Related Art
Hydrogen is a very attractive fuel because it is renewable and can be used to efficiently produce electricity in a fuel cell with no harmful emissions. A hydrogen fuel cell is an electro-chemical device that includes an anode and a cathode with an electrolyte therebetween. The anode receives hydrogen gas and the cathode receives oxygen or air. The hydrogen gas is dissociated at the anode catalyst to generate free protons and electrons. The protons pass through the electrolyte to the cathode. The protons react with the oxygen and the electrons at the cathode catalyst to generate water. The electrons from the anode cannot pass through the electrolyte, and thus are directed through a load to perform work before being sent to the cathode.
Proton exchange membrane fuel cells (PEMFC) are a popular fuel cell for vehicles. The PEMFC generally includes a solid polymer electrolyte proton conducting membrane, such as a perfluorosulfonic acid membrane. The anode and cathode electrodes, or catalyst layers, typically include finely divided catalytic particles, usually platinum (Pt), supported on carbon particles and mixed with an ionomer. The catalytic mixture is deposited on opposing sides of the membrane. The combination of the anode catalytic mixture, the cathode catalytic mixture and the membrane define a membrane electrode assembly (MEA). Each MEA is usually sandwiched between two sheets of porous material, the gas diffusion layer (GDL), that protects the mechanical integrity of the membrane and also helps in uniform reactant and humidity distribution. MEAs are relatively expensive to manufacture and require certain conditions for effective operation.
Several fuel cells are typically combined in a fuel cell stack to generate the desired power. For example, a typical fuel cell stack for a vehicle may have two hundred or more stacked fuel cells. The fuel cell stack receives a cathode input gas, typically a flow of air forced through the stack by a compressor. The fuel cell stack also receives an anode hydrogen input gas that flows into the anode side of the stack. Not all of the oxygen is consumed by the stack and some of the air is output as a cathode exhaust gas that may include water as a by-product of the chemical reaction taking place in the stack.
The fuel cell stack includes a series of bipolar plates positioned between the several MEAs in the stack, where the bipolar plates and the MEAs are positioned between two end plates. The bipolar plates include anode side and cathode side flow distributors, or flow fields, for adjacent fuel cells in the stack. Anode gas flow channels are provided on the anode side of the bipolar plates that allow the anode reactant gas to flow to the respective MEA. Cathode gas flow channels are provided on the cathode side of the bipolar plates that allow the cathode reactant gas to flow to the respective MEA. One end plate includes anode gas flow channels, and the other end plate includes cathode gas flow channels. The bipolar plates and end plates are made of a conductive material, such as stainless steel or a conductive composite. The end plates conduct the electricity generated by the fuel cells out of the stack. The bipolar plates also include flow channels through which a cooling fluid flows.
When a fuel cell system is shutdown, the stack can either be left with an excess of hydrogen or oxygen, or the system can attempt to simultaneously consume both reactants. In the first case, unreacted hydrogen gas remains in the anode side of the fuel cell stack. This hydrogen gas is able to diffuse through or cross over the membrane and react with the oxygen on the cathode side of the stack. As the hydrogen gas diffuses to the cathode side, the total pressure on the anode side of the stack is reduced. Some oxygen will be left in the cathode plumbing, and will slowly re-enter the cathode flowfield, either by convective or diffusive forces. Most of it will react with hydrogen that is locally present in the cell. Eventually, the local hydrogen in a cell will be consumed, and oxygen will start to concentrate. Eventually, oxygen will locally permeate the membrane to the anode.
When the air enters the anode side of the stack it generates an air/hydrogen front that creates a short circuit in the anode side, resulting in a lateral flow of hydrogen ions from the hydrogen flooded portion of the anode side to the air-flooded portion of the anode side. The lateral current combined with the high lateral ionic resistance of the membrane produces a significant lateral potential difference (˜0.5 V) across the membrane. A locally high potential is produced between the cathode side opposite the air-filled portion of the anode side. The high potential adjacent to the electrolyte membrane drives rapid carbon corrosion, and causes the electrode carbon layer to thin. This decreases the support for the catalyst particles, which decreases the performance of the fuel cell.
In automotive applications, there are a large number of start and stop cycles required over the life of the fuel cell system, each of which may generate an air/hydrogen front as described above. Targets of 40,000 start and stop cycles would be considered reasonable. Leaving a stack in an oxygen-rich atmosphere at shutdown results in a damaging air/hydrogen event at both shutdown and startup, where 2 to 5 μV of degradation per start and stop cycle is plausible. Thus, the total degradation over 40,000 start and stop cycle events is on the order of 100 or more mV. If the stack is left with a hydrogen/nitrogen mixture at shutdown, and the system is restarted before appreciable concentrations of oxygen have accumulated, cell corrosion during the shutdown and subsequent restart is avoided.
It is known in the art to purge the hydrogen gas out of the anode side of the fuel cell stack at system shutdown by forcing air from the compressor into the anode side at high pressure. However, the air purge creates an air/hydrogen front that causes at least some corrosion of the carbon support, as discussed above. Another known method in the art is to provide a cathode re-circulation to reduce carbon corrosion at system shutdown, as described in the commonly owned U.S. non-provisional patent application titled, “Method for Mitigating Cell Degradation Due to Startup and Shutdown Via Cathode Re-Circulation Combined with Electrical Shorting of Stack,” U.S. Ser. No. 11/463,622, filed Aug. 10, 2006, which is incorporated herein by reference. Particularly, it is known to pump a mixture of air and a small amount of hydrogen through the cathode side of the stack at system shutdown so that the hydrogen and oxygen combine in the cathode side to reduce the amount of oxygen, and thus the potential that causes carbon corrosion.
It is also known to stop the cathode air flow while maintaining positive anode side hydrogen pressure at shutdown, and to then short the stack to allow the oxygen to be consumed by hydrogen, followed by closing the inlet and outlet valves of the anode and cathode sides, as described in the commonly owned U.S. non-provisional patent application titled, “Method of Mitigating Fuel Cell Degradation Due to Startup and Shutdown Via Hydrogen/Nitrogen Storage,” U.S. Ser. No. 11/612,120, filed Dec. 18, 2006, which is incorporated herein by reference.
While it has been shown that these techniques do help to mitigate corrosion of the carbon support, these techniques may not remove all of the oxygen and may require additional components for a cathode recycle. Furthermore, the valves may not be leak tight, and the cooling of the gas and water vapor condensation after shutdown creates a vacuum which pulls air into the stack. Therefore, there is a need in the art to maintain adequate hydrogen concentration during fuel cell system off times to prevent oxygen from accumulating in the fuel cell stack. Furthermore, there is a need to limit the amount of hydrogen and electrical power consumed while maintaining adequate hydrogen concentrations needed for mitigation.